Working of non-ferrous metals

ABSTRACT

UTILIZING A PHENOLIC COMPOUND IN WHICH THE HYDROXYL IS ATTACHED DIRECTLY TO THE PHENOL NUCLEUS AS A LUBRICANT IN THE WORKING OF NON-FERROUS METAL.

United States Patent O 3,794,595 WORKING OF NON-FERROUS METALS Edwin J. Latos, Chicago, Ill., assignor to Universal Oil Products Company, Des Plaines, Ill. No Drawing. Filed May 8, 1972, Ser. No. 251,308 Int. Cl. C10m 1/20 US. Cl. 252-42.1 10 Claims ABSTRACT OF THE DISCLOSURE Utilizing a phenolic compound in which the hydroxyl is attached directly to the phenol nucleus as a lubricant in the working of non-ferrous metal.

BACKGROUND OF THE INVENTION In the working of metal, wherein two metal surfaces are in movable contact with each other, a lubricant is needed to serve as an antiwear and antiseize agent, as Well as a coolant. The requirements for a satisfactory lubricant in the working of ferrous metals are not as severe as in the case of non-ferrous metals. Accordingly, the prior art is replete with numerous lubricants for use with ferrous metals and these lubricants include oil, fat, grease, soaps, detergents, emulsions, etc. However, these lubricants generally are not satisfactory for use in the working of nonferrous metals and particularly zirconium, titanium and alloys thereof.

DESCRIPTION OF THE INVENTION In accordance with the present invention, lubrication of non-ferrous metals is accomplished by utilizing a lubricant comprising a phenolic compound in which the hydroxyl is attached directly to the phenol nucleus. In a preferred embodiment, the phenolic compound is an alkyl phenol in which the alkyl group contains from 1 to 24 and still more particularly from 5 to 12 carbon atoms. The phenolic compound may be utilized alone or in admixture with other suitable lubricating ingredients.

While the lubricant set forth in the present invention is particularly advantageous for use in the working of nonferrous metals, it is understood that the lubricant also may be utilized to advantage in the working of ferrous metals. The working of the metal may take various forms including drawing, rolling, extruding, cutting, drilling, broaching, tapping, threading, etc. In one embodiment, the lubricant set forth herein is of especial advantage for use in tube'reducing or similar operations.

In addition to serving as an antiwear and anti-seizure agent, the lubricant must survive the chemical and thermal environment at the interface to avoid formation of wear debris which is difiicult to remove from the finished article. The lubricant also must avoid corrosion of the metal, staining and must not excessively alter the surface structure of the metal. This latter requirement is particularly important in the case of zirconium and titanium because of the desirability to prevent formation of the open grain surface.

While the method of the present invention is particularly applicable for the working of zirconium, titanium or alloys thereof, it is understood that it also may be used to advantage in the working of other non-ferrous metals including, for example, aluminum, copper, brass, bronze, magnesium, etc.

In one embodiment, the lubricant for use in the present invention is phenol but preferably is an alkyl phenol in which the alkyl group contains from 1 to 24 and preferably from 5 to 12 carbon atoms. Illustrative examples in this embodiment of the preferred alkyl phenols comprise pentylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, with the alkyl group being in the ortho, meta or preferably in the para position, or mixture thereof. Other alkyl phenols included in this embodiment comprise methylphenol, ethylphenol, propylphenol, butylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, eicosylphenol, again with the alkyl group being in the ortho, meta or preferably in the para position. The alkyl group may be of primary, secondary or tertiary configuration.

In another embodiment, the phenolic compound contains two or more alkyl groups of from 1 to 20 carbon atoms each. In one embodiment, the alkyl groups are of the same chain length and in another embodiment the alkyl groups are of different chain length. With two alkyl groups, these may be in the positions 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-positions. With three alkyl groups, the alkyl groups may be in the positions 2,3,4-, 2,3,5, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-positions. Illustrative examples of phenolic compounds in these embodiments include 2,4-dibutylphenol, 2,5-diamylphenol, 2,6-dioctylphenol, Z-methyl 4 octylphenol, 2-methyl-6-nonylphenol, 2,4,6-trimethylphenol, 2, 4,6-triethylphenol, 2,4,6-tributylphenol, 2,6-dimethyl-4- octylphenol, 2,6-dimethyl-4-nonylphenol, 2-butyl-4,6-dimethylphenol, 2,6-dibutyl-4-methylphenol, etc. It is understood that these specific compounds are illustrative only and not intended to be limiting, that the alkyl groups may be of primary, secondary and/or tertiary configuration and that a mixture of the monoand/or polyalkyl phenols may be used.

In still another embodiment, the phenolic compound may contain other substituents attached to the phenolic ring. These substituents may contain halogen, sulfur, oxygen, etc. Of the halogen substituents, chlorine is preferred, the other halogens being bromine, iodine and/or fluorine. The sulfur may be in the form of mercapto, thioether, heterocyclic sulfur, etc. The nitrogen may be in the form of amine, alkylamine or dialkylamine in which the alkyl contains from 1 to about 10 carbon atoms each, heterocyclic nitrogen, etc. The other oxygen may be as hydroxyl, ether, carbonyl, heterocyclic oxygen, etc. It is understood that these variously substituted phenolic compounds are not necessarily equivalent.

As hereinbefore set forth, the phenolic compound set forth herein may be used in admixture with other lubricating ingredients and may be in the form of a solution or emulsion. In one embodiment, the other ingredient comprises a fatty acid and particularly oleic acid. Other fatty acids include decylenic, dodecylenic, palmitoleic, ricinoleic, petroselinic, vaccenic, linoleic, linolenic, eleostearic, licanic, parinaric, gadoleic, cetoleic, selacholeic, etc., as illustrative of unsaturated fatty acids and butyric, isovaleric, caproic, caprylic, capric, lauric,

myristic, palmitic, stearic, arachidic, behenic, lignoceric, cerotic, etc., as illustrative of saturated fatty acids. In another embodiment, the lubricating composition may contain mineral oil, sulfonated oil, alcohols, ethers, fatty acid esters, alkanolamine soaps of fatty acids, alkali metal soaps of fatty acids, salts, organic nitrates, inorganic nitrates, organic phosphates, inorganic phosphates, various water based lubricants, etc. When the additional ingreclient does not form a solution with the phenolic compound, the composition may be utilized as an emulsion, either with or without water. In general, these additional ingredients will be selected from those described in the prior art. The phenolic compound may be used in these compositions in the range of from about 1% to about 99% and preferably from about to about 80% by weight of the final composition, exclusive of water or solvent utilized in the final composition.

The lubricant of the present invention is utilized in conventional manner, which will depend on the particular procedure employed in the working of the metal. In any event, the lubricant must be applied in a manner that it will be present at the points of contact of the metals in moving relationship to each other. Also, the amount of lubricant will be suificient to accomplish effective lubrication, which amount also will depend upon the particular working procedure employed.

As hereinbefore set forth, effective lubrication of nonferrous metals is accomplished by utilizing a phenolic compound having the hydroxyl directly attached to the phenol nucleus. The phenolic compound may be used alone or in admixture with other ingredients as described hereinbefore.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I The lubricants were evaluated in a modified Bowden- Leben pin and disc machine. The Bowden-Leben method is described in The Friction and Lubrication of Solids, 1954, p. 74, by Bowden and Tabor. This method is also discussed in the article by E. Rabinowicz, entitled The Boundary Friction of Very Well Lubricated Surfaces, which was presented at the A.'S.L.E. Ninth Annual Meeting in Cincinnati on Apr. 5, 1954, and published in the July-August 1954 issue of Lubricating Engineering. In the modification used for the runs reported herein, a polished A-8 steel disc rotates in contact with an upwardly extended rounded Zircaloy pin. Zircaloy No. 2, for example, is an alloy comprising 98.3% by weight zirconium, 1.5% by weight tin, 0.20% by weight iron and 0.10% by weight chromium.

A total of about 2 g. of lubricant is utilized. About 1.8 g. of lubricant is applied to the disc and about 0.2 g. of lubricant is applied to the pin. The equipment is enclosed in a housing which is heated for varying the temperature of the run which, in these evaluations, can be within the range of from 72 to 212 F. The speed is fixed at 6 r.p.m. In each run an original load of 100 g. is increased in units of 100 g. at intervals of 1.67 minutes to a maximum load of 1300 g. A strain gage circuit is used as sensing element in converting the frictional effects into equivalent electrical responses, which then are recorded on a continuous chart recorder. The coeflicient of friction is determined for each time interval. In addition, the diameter of the wear spot on the pin is measured. The pin and disc are visually inspected immediately after the test to determine the amount of debris.

The following table reports runs made using nonylphenol as the lubricant and a run using a mixture of 90% nonylphenol and 10% oleic acid. For comparative purposes, the table also reports the results of a run using oleic acid alone as the lubricant. These runs were made at a temperature of 212 F.

TABLE I Lubricant nonylp y Time, Nonyl- 10% oleic Oleic min phenol aci acid Load, g

1. 67 0. 175 0. 109 0. 100 200 3. 34 0. 142 0. 092 0. 087 300 5. 01 0. 142 0. 072 0. 084 0. 142 0. 067 0.077 0. 142 0. 060 0. 075 0. 139 0. 063 0. 072 0. 140 0. 064 0. 073 0. 144 0. 063 0. 070 0. 142 0. 063 0. 073 0. 139 0. 066 0. 074 0. 127 0. 066 0. 071 0. 126 0. 065 0. 070 0. 123 0. 065 0. 069 0. 112 0. 066 O. 069 0. 111 0. 067 0. 067 0. 107 0. 066 0. 067 0. 097 0. 062 0. 065 0. 095 0. 064 0. 064 0. 098 0. 062 0. 064 0. 092 0. 058 O. 065 0. 091 0. 056 0. 066 0. 092 0. 056 0. 078 0. 099 0. 055 0. 078 0. 097 0. 056 0. 078 0. 098 0. 060 0. 074 Debris Wear area, mm. 0. 181 0. 126 0.283

1 Light to moderate.

2 Very light.

3 Moderate.

From the data in the above table, it will be noted that the coefficient of friction was satisfactory in all of the runs. In the run using nonylphenol neat, the debris was light to moderate and the wear was low. When using the mixture of nonylphenol and oleic acid, the debris was even less and the wear was even lower. The run using oleic acid alone produced more debris and much higher wear.

EXAMPLE II The lubricant used in this example is octylphenol, which was evaluated in the same manner as described in Example I. The coefiicient of friction decreased from 0.125 to 0.111 after 202 minutes and a load of 1300 g. The wear area was 0.181 mm. and the debris was light to moderate.

EXAMPLE III The lubricant used in this example is dodecylphenol and the evaluation was made in the same manner as described in Example I. The coefiicient decreased from 0.150 to 0.095 after 202 minutes and a load of 1300 g. The debris again was light to moderate and the wear area was 0.138 mm.

EXAMPLE IV An additional evaluation was made in the same manner as described in Example I but using a mixture of 90% nonylphenol and 10% stearic acid. The coetficient of friction decreased from 0.084 to 0.067 during the run of 202 minutes. The amount of debris was light and the wear area was 0.196 mm.

EXAMPLE V Another evaluation was made in the same manner as above but using an emulsion of 30% by weight of octylphenol, 10% by weight of potassium stearate and 60% by weight of water as the lubricant. The coefiicient of friction decreased from 0.134 to 0.053. The amount of debris was light and the wear area was 0.138 mmf EXAMPLE VI Another evaluation was made using a mixture of 90% by weight nonylphenol and 10% by weight of Neustrene 060 (a refined hydrogenated tallow glyceride) as the lubricant in the same manner as described in the previous examples. The coefficient of friction decreased from 0.117 to 0.095. The amount of debris was light and the wear area was 0.138 mmfi. In contrast, another run using only the Neustrene 0.60 as the lubricant formed more debris which is described as being moderate.

EXAMPLE VII An evaluation was made in the same manner as hereinbefore described using a mixture of 50% nonylphenol and 50% by weight of mineral oil. The mineral oil is available commercially as Sentry 20 and is a solvent extracted neutral oil having a viscosity, SUS, of 205 at 100 F. The coefficient of friction in this run decreased from 0.134 to 0.089 after 202 minutes and a final load of 1300 g. The debris was light and the wear area was 0.166 mm?. In another run using only the mineral oil, the amount of debris was described as heavy.

EXAMPLE VHI As hereinbefore set forth, it is an essential feature of the present invention that the hydroxyl group is attached directly to the phenol nucleus. This criticality is demonstrated in a run in which oxyethylated nonlyphenol containing 9-10 oxyethylene groups was used as the lubricant. This oxyethylated nonylphenol is available commercially as Triton X-lOO. When used as a lubricant and evaluated in the same manner as described in the previous examples, considerable debris was formed and the wear area was 0.273 mm.

EXAMPLE IX Nonylphenol neat and a blend of 90% nonylphenol and oleic acid were each used in a tube reducing operation in which a Zircaloy tube was reduced in a series of multiple reduction steps. In both cases, the desired reduction was obtained with no debris on the tube and only a small amount of debris on the mandrel. The small amount of debris was readily removable by rinsing in a hydrocarbon or alcohol. A nonlyphenol-potassium stearate emulsion also was evaluated in the same manner and gave substantially the same results.

I claim as my invention:

1. In the working of metal, wherein said metal is in movable contact with another metal, the method which comprises applying to the points of contact of said metals 6, in moving relationship to each other as a lubricant, an alkyl phenol in which the hydroxyl is attached directly to the phenol nucleus.

2. The method of claim 1 in which said metal is a nonferrous metal.

3. The method of claim 2 in which said metal is zirconium, alloy thereof, titanium or alloy thereof.

4. The method of claim 1 in which said alkyl contains from 1 to 24 carbon atoms.

5. The method of claim 4 in which said alkyl contains from 5 to 12 carbon atoms.

6. The method of claim 4 in which said phenolic compound is in admixture with a fatty acid.

7. The method of claim 6 in which said mixture comprises from about 1% to about 99% by weight of nonylphenol and from about 1% to about 99% by weight of oleic acid.

8. The method of claim 1 in which said phenolic compound is used as an emulsion with an alkali metal soap and water.

9. The method of claim 1 in which said working is a tube reducing operation.

10. The method of claim 9 in which a zirconium alloy is subjected to a tube reducing operation.

References Cited UNITED STATES PATENTS 2,780,598 2/ 1957 Cafcas 25242.1 X 2,811,489 10/1957 Laug 252-49.5 X 2,914,477 11/1959 Cafcas 252-495 X 3,640,856 2/1972 Alund 252-495 X 2,976,160 3/1961 Fronczak et al. 252-495 X 3,123,561 3/1964 Rue 252-49.5 X 2,447,475 8/1948 Kaberg et al 252-495 X 2,987,480 6/1961 Talley 252-52 R 3,365,397 1/ 1968 Kolarik 25249.5 X 3,432,434 3/1969 Armstrong et al. 25249.5

HELEN M. S. SNEED, Primary Examiner US. Cl. X.R. 

